|Número de publicación||US4248977 A|
|Tipo de publicación||Concesión|
|Número de solicitud||US 05/958,523|
|Fecha de publicación||3 Feb 1981|
|Fecha de presentación||7 Nov 1978|
|Fecha de prioridad||7 Nov 1978|
|También publicado como||CA1121933A1|
|Número de publicación||05958523, 958523, US 4248977 A, US 4248977A, US-A-4248977, US4248977 A, US4248977A|
|Inventores||William E. Wertz|
|Cesionario original||The Polymer Corporation|
|Exportar cita||BiBTeX, EndNote, RefMan|
|Citas de patentes (12), Citada por (10), Clasificaciones (8), Eventos legales (1)|
|Enlaces externos: USPTO, Cesión de USPTO, Espacenet|
1. Field of the Invention
This invention relates to thermoplastic coating powders adapted to be applied by fusion coating processes and more particularly to thermoplastic coating powders that have improved adhesion to substrates.
2. Description of the Prior Art
Fusion coating processes are those in which a powdered coating material is distributed over a substrate and is heated to cause the powders to fuse into a continuous protective or decorative film. The fluidized bed and the electrostatic spray coating processes are representative of fusion coating processes.
Fusion coating processes are attractive alternatives to solution coatings since solvents are not required. Not only is the cost of solvents saved, but, more importantly, the need for collection and recovery systems to guard against fire, explosions and contamination of the atmosphere is eliminated.
Except in those specialized circumstances in which stripable coatings are desired, the performance of a protective or decorative coating is dependent upon the tenacity with which the coating material adheres to its substrate. Adhesion is necessary to prevent the coating material from being peeled away from the substrate and to protect the substrate from the spread of underfilm corrosion should any discontinuity in the coating layer occur.
It has long been recognized that the adhesion between a coating and a substrate can be very much improved through the use of primers. In recent years primers, variously comprised of reactive thermosetting resins and thermoplastic adhesives have been specially adapted for use in connection with fusion coating processes. Unhappily, these primers are applied to the substrate by solution coating techniques and so, in addition to being a time consuming and bothersome step, some of the advantage of using the solventless fusion coating processes is lost since a solvent recovery system may be required.
To avoid having to prime a substrate, it has been proposed to mix adhesion promoting materials directly into coating powders. For example, U.S. Pat. No. 3,562,205 discloses the use of organic nitrogen compounds and metal fillers to improve the adhesion of thermoplastic coating powders to a substrate. It is known that reactive epoxy resins are useful in improving the ability of nylon to adhere to a substrate. It is also known that the adhesion of nylon coating powders is greatly improved by dry blending a reactive epoxy, a curing agent for the epoxy and a polyvinyl acetal into the powder.
While the inclusion of an epoxy resin, a curing agent, and a polyvinyl acetal as dry blend additives to nylon coating powders will provide markedly improved adhesion, coating powders based upon dry blends are not preferred. Quite generally, dry blends are not satisfactory for use in electrostatic coating processes since the separate components of a dry blend coating powder will differ in their ability to accept a charge, which may lead to disuniformities in the coating. Dry blends may prove unsatisfactory for use in fluidized bed coating processes since the separate components will be removed from the fluidized bed at different rates depending upon such factors as their size, shape, softening point, and density. For these reasons, the higher quality coating powders used in heat fusion processes are prepared by melt mixing the fillers, pigments, stabilizers, plasticizers, etc. into the powder. Most commonly this is done by processing the several raw materials in a mixing extruder, extruding small diameter rods, chopping the rods into pellets and grinding the pellets to the required size.
Attempts to melt mix an epoxy, a curing agent and a polyvinyl acetal with nylon in an extruder have failed since, at the temperature at which the nylon melts, the epoxy becomes reactive and fuses the entire system together into an intractable and useless mass. For this reason, the utility of this preferred system for improving the adhesion of a nylon coating powder has been seriously limited.
Accordingly, it is an object of this invention to improve the adhesion between a substrate and a fused nylon powder coating.
Another object of this invention is to provide melt mixed, homogenous nylon coating powders that, when fused, will adhere to a substrate.
Briefly, these and other objects of this invention are achieved by melt blending minor amounts of a reactive epoxy resin and a polyvinyl acetal into a nylon coating powder while omitting an epoxy curing agent from the formulation. It has been discovered, somewhat predictably, that most epoxies will not react at the melting point of the nylon in the absence of a curing agent for the epoxy; it has been discovered, quite surprisingly, that the omission of the curing agent does not observably reduce the adhesion of the nylon coating powders to a substrate.
The selection of an epoxy resin for use in this invention is not critical and may include epoxy resins having an epoxide equivalent weight of from about 200 to over 2,000. The particular epoxy may be selected, for example, with regard to its melt viscosity so that it may be used to raise or lower the melt viscosity of the coating powders. Quite generally, the additions of expoxies having an epoxy equivalent weight of between 200 to 2,000 and in an amount of from about 2 to 15 parts by weight per 100 parts of nylon have proved useful.
The polyvinyl acetal resins which have been used in the practice of this invention have been limited to those that can readily be obtained in the marketplace which are polyvinyl butyral and polyvinyl formal, although there is no reason to believe that others might not be effective. The polyvinyl acetals are commonly prepared by the saponification of polyvinyl acetate to yield polyvinyl alcohol which, in turn, is acetalated with formaldehyde or butyraldehyde. The resulting resins predominate in polyvinyl acetal with minor residues of polyvinyl alcohol and polyvinyl acetate in the polymeric chain. Polyvinyl acetals are available, for example, from Monsanto under their trademarks Butvar and Formvar and from Farbwerke Hoechst under its trademark Mowital. The inclusion of from about 1 to 10 parts by weight polyvinyl acetal per 100 parts nylon have proved effective.
The nylons that are found most useful in the practice of this invention as coating powders are types 11 and 12 nylon which, due to their lower melting point, make better coating materials than the more common types 6 and 6/6 nylon.
The following materials were premixed in a Henschel blender:
______________________________________ Parts Per 100 Material By Weight______________________________________Nylon 11 Molding Resin (Rilsan BMNO) 100Epoxy Resin-450-550EEW (Epon 1001) 7Polyvinyl Butyral (Mowital B30H) 3CaCO3 Filler (Hydrocarb) 90) 20TiO2 -Pigment 8______________________________________
The blended materials were then extruded at a die temperature of 400° F. into 1/8 inch rods which were diced into pellets. The pellets were then cryogenically ground to minus 60 mesh for use in a fluidized bed.
The above powders were fluidized and cleaned and degreased 3"×4" steel panels were preheated to 575° F. and coated in the fluidized bed to form an 8 mill fused coating over the panels. The panels were scored with a knife by cutting two intersecting lines in the form of an "X" through the coating down to the surface of the panel.
The panels so prepared were subjected to a continuous spray of salt water having a slat concentration of 5 percent and held at a temperature of about 100° F. These panels were observed at periodic intervals and withstood 1,000 hours of exposure without any observable change in the adhesion of the coating to the panel and without evidence of any underfilm corrosion.
By way of comparison, nylon coatings were applied by a fluidized bed to panels in a manner similar to that discussed above except that no epoxy or polyvinyl acetal was mixed with the nylon. In the tests so performed, it was found that adhesion was lost in less than 24 hours.
|Patente citada||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US2713567 *||14 Abr 1952||19 Jul 1955||Shell Dev||Composition containing glycidyl polyether and a polyvinyl acetal resin|
|US3058951 *||23 Jun 1959||16 Oct 1962||Gen Electric||Composition comprising an epoxy resin, a polyvinyl acetal resin, and a polyacrylate resin, and an article coated therewith|
|US3098054 *||20 Nov 1959||16 Jul 1963||Gen Electric||Composition comprising epoxy resin, polyvinyl acetal, silica, and a bf3-amine complex|
|US3449280 *||27 Abr 1960||4 Oct 1983||Título no disponible|
|US3462337 *||1 Feb 1968||19 Ago 1969||Du Pont||Polyamide-polyepoxide cross-linked reaction product adhesive composition and method of uniting metal surfaces using same|
|US3562205 *||12 May 1969||9 Feb 1971||Polymer Corp||Coating composition for adhering synthetic resins to metal substrates|
|US3657380 *||9 Dic 1969||18 Abr 1972||Du Pont||High temperature resistant coating composition of an aromatic polyamide and an epoxy resin|
|US3673273 *||3 Jul 1968||27 Jun 1972||Scholven Chemie Ag||Plastic of polyamide and epoxy resin|
|US3678127 *||19 Oct 1970||18 Jul 1972||Ciba Geigy Ag||Carboxy terminated polyamides and diepoxides|
|US3880947 *||18 Dic 1973||29 Abr 1975||Ford Motor Co||Powder coating compositions including carboxyl terminated polyamide crosslinking agents|
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|Patente citante||Fecha de presentación||Fecha de publicación||Solicitante||Título|
|US4309512 *||3 Dic 1980||5 Ene 1982||Tokyo Shibaura Denki Kabushiki Kaisha||Heat-resistant thermosetting resin composition|
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|US4500606 *||16 Nov 1983||19 Feb 1985||Ashland Oil, Inc.||Sealer for polyester and method of use to obtain laminates|
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|US5453295 *||15 Ene 1992||26 Sep 1995||Morton International, Inc.||Method for preventing filiform corrosion of aluminum wheels by powder coating with a thermosetting resin|
|US5770654 *||20 Mar 1997||23 Jun 1998||E. I. Du Pont De Nemours And Company||Polyamide compositions toughened with waste plasticized polyvinylbutyral|
|US6027814 *||27 Dic 1995||22 Feb 2000||Elf Atochem S.A.||Pulverulent polyamide composition for the coating of metal substrates|
|US8865053 *||21 Mar 2005||21 Oct 2014||Evonik Degussa Gmbh||Process for the production of moldings|
|CN101519544B||3 Abr 2009||22 Ago 2012||丹阳市科瑞特粉末新材料有限公司||Ultra-low temperature epoxy resin nylon hybrid thermosetting powder coating and method for preparing same|
|EP0293292A1 *||24 May 1988||30 Nov 1988||Elf Atochem S.A.||Polyamide coating powders and substrate covered by these coating powders|
|Clasificación de EE.UU.||525/58, 524/904|
|Clasificación internacional||C09D5/03, C09D177/00, C08L77/00|
|Clasificación cooperativa||Y10S524/904, C09D177/00|
|13 Jul 1987||AS||Assignment|
Owner name: MORTON THIOKOL, INC., A DE CORP
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:POLYMER CORPORATION, THE, A PA CORP.;REEL/FRAME:004736/0904
Effective date: 19870701